The objective of this study is to compare the performance of cathode electrode in photocatalytic fuel cell (PFC) system under UV light irradiation. The initial concentration 10 mg/L of Reactive Black 5 (RB5) with carbon plate (CP) and Pt-loaded carbon (Pt/C) as cathode reduced to 2.052 and 0.549 mg/L, respectively, after 24 h irradiated by UV light. The value for open circuit voltage, Voc, short-circuit current density, Jsc and maximum power density, Pmax for CP was 0.825 V, 0.00035 mA/cm2 and 0.000063 mW/cm2, respectively, meanwhile Voc, Jsc and Pmax for Pt/C was 1.15 V, 0.0015 mA/cm2 and 0.000286 mW/cm2, respectively, by varying external resistor value from 300 kΩ to 10 Ω. The degradation of RB5 and generation of electricity with Pt/C as cathode showed greater performance than CP.